4-dimethylaminobenzylidene-4-chloroaniline | 1624-45-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-dimethylaminobenzylidene-4-chloroaniline
• 英文别名: 4-chloro-N-[4-(dimethylamino)benzylidene]aniline
• CAS: 1624-45-9
• 化学式: C₁₅H₁₅ClN₂
• 分子量: 258.75
• InChiKey: PWFDYJSIDJXQFU-GZTJUZNOSA-N

物化性质

• 熔点：
  149.5-150.5 °C
• 沸点：
  401.4±30.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

反应信息

• 作为产物：
  描述：

  以 苯 为溶剂， 生成 4-dimethylaminobenzylidene-4-chloroaniline
  参考文献：
  名称：

  Mechanism of thermal Z/E isomerization of substituted N-benzylideneanilines. Nature of the activated complex with an sp-hybridized nitrogen atom

  摘要：

  In order to study the mechanism of thermal geometrical isomerization involving a sp2-hybridized nitrogen atom, kinetic effects of substituent, solvent, and pressure were studied in substituted N-benzylideneanilines. The effect of the substituent on the aniline moiety was almost independent of the electronic nature of the benzylidene group, and the results could be described satisfactorily by log (k/k(o)) = rho[sigma-degrees + r+(sigma+-sigma-degrees)+ r-(sigma--sigma-degrees)], except for the 4-(dimethylamino) group. The r- values were more than twice as large as r+, suggesting strongly that the aniline ring is in conjugation not with the carbon-nitrogen pi bond but with the nitrogen lone pair in the transition state. The lower activation enthalpies and fairly large negative activation entropies observed in N-(4-X-benzylidene)4-nitroanilines also support this view. When a dimethylamino group exists in the 4-position of the aniline ring, the rate constants observed were larger than that expected from the above equation. This deviation suggests the existence of a reaction route where the two phenyl groups become coplanar in the transition state. Ab initio calculations on selected N-phenylformaldimines and N-benzylideneanilines were performed to characterize the actual relation between both reaction possibilities as alternative and parallel routes, respectively. On the basis of the experimental data, the rate constants for the two inversion isomerizations were estimated by assuming parallel reactions for three cases.

  DOI：

  10.1021/jo00068a042

文献信息

• C—H...π, π–π and C—H...Cl interactions in chloro-substituted Schiff bases and 4-chloro-<i>N</i>-[4-(dimethylamino)benzylidene]aniline
  作者：Xiu-Li You、Cheng-Rong Lu、Yong Zhang、De-Chun Zhang

  DOI：10.1107/s0108270104017871

  日期：2004.9.15

  Molecular packing analyses were carried out on 15 crystal data sets of chloro-substituted Schiff bases, including that of the title compound, C15H15ClN2. C-H...pi and pi-pi interactions play a major role in the molecular self-assembly in the crystal. The former interactions favor molecules assembling into a screw, with a non-centrosymmetric crystal structure. When the molecular dipole is small, pi-pi interactions favor a parallel, but not usually antiparallel, mode of packing. Weak C-H...X hydrogen bonds (X = Cl or Br) and X...X interactions seem to be a secondary driving force in packing. The title molecule takes the trans form and the two benzene rings are twisted around the central linkage in opposite directions. In the crystal structure, molecules interact through C-H...pi and pi-pi interactions, forming a 'dimer' and further forming double chains along [001]. The double chains are extended along [101] through C-H...Cl hydrogen bonds, forming double layers in (010). In the third direction, there are only ordinary, weaker, van der Waals interactions, which explains the crystal habit (i.e. thin plate).
• Tiwari, Vivek; Singhai, Rashmi; Mishra, Journal of the Indian Chemical Society, <hi>2004</hi>, vol. 81, # 2, p. 147 - 149
  作者：Tiwari, Vivek、Singhai, Rashmi、Mishra

  DOI：——

  日期：——